Continuous process for scrubbing so2 from a gas stream with h2 regeneration and co2 stripping

ABSTRACT

AN INPUT GAS STREAM CONTAINING SO2 IS CONTINUOUSLY TREATED IN ORDER TO REMOVE A SUBSTANTIAL PORTION OF THE SO2 THEREFROM BY THE STEPS OF: (A) SCRUBBING THE INPUT GAS STREAM WITH AN AQUEOUS ABSORBENT STREAM CONTAINING AN ALKALINE REAGENT; (B) TREATING THE RESULTING RICH ABSORBENT STREAM WITH A GASEOUS MIXTURE OF H2S AND CO2 AT CONDITIONS SELECTED TO CONVERT THE SULFITE COMPOUND CONTAINED THEREIN TO THE CORRESPONDING THIOSULFATE COMPOUND AND TO PRODUCE A GAS STREAM ENRICHED IN CO2 CONTENT; (C) CATLYTICALLY REACTING THE RESULTING THIOSULFATE COMPOUND WITH HYDROGEN AT REDUCTION CONDITIONS SELECTED TO PRODUCE A LIQUID STREAM CONTAINING THE CORRESPONDING SULFIDE COMPOUND; (D) ADDING CO2 TO THE GAS STREAM FROM STEP (B) TO MAKE A STRIPPING GAS; (E) STRIPPING HYDROGEN SULFIDE FROM THE LIQUID STREAM PRODUCED IN STEP (C) BY COUNTERCURRENTLY CONTACTING THE LIQUID STREAM WITH THE RESULTING STRIPPING GAS TO FORM A REGENERATED AQUEOUS ABSORBENT STREAM AND AN OVERHEAD GAS STREAM CONTAINING H2S AND CO2; (F) PASSING AT LEAST A PORTION OF THE REGENERATED ABSORBENT STREAM TO THE SCRUBBING STEP AND (G) PASSING AT LEAST A PORTION OF THE OVERHEAD GAS STREAM FROM STEP (D) TO STEP (B). THE PRINCIPAL UTILITY OF THIS SCRUBBING PROCESS IS ASSOCIATED WITH THE PROBLEM OF CONTINUOUSLY REMOVING A SULFUR DIOXIDE CONTAMINANT FROM THE FLUE OR STACK GAS STREAMS SUCH AS ARE TYPICALLY PRODUCED IN MODERN ELECTRICAL POWER GENERATING STATIONS IN ORDER TO ABATE A SERIOUS POLLUTION PROBLEM AND TO ENABLE THE SAFE, NONPOLLUTING BURNING OF HIGH SULFUR FUELS. KEY FEATURES OF THIS PROCESS ARE: SELECTIVE CONVERSION OF THE SULFITE COMPOUND OBTAINED FROM THE SCRUBBING STEP TO THE CORRESPONDING THIOSULFATE COMPOUND IN THE PRELIMINARY TREATMENT STEP USING A PORTION OF A SUBSEQUENTLY PRODUCED H2S PRODUCT STREAM, REDUCTION OF THE RESULTING THIOSULFATE COMPOUND TO THE CORRESPONDING SULFIDE COMPOUND IN A HIGHLY EFFICIENT ECONOMIC AND SELECTIVE MANNER, STRIPPING OF H2S WITH A SPECIALLY PREPARED CO2 STREAM, MINIMIZATION OF UNDESIRED SULFATE BY-PRODUCTS DURING ALL OF THESE CONVERSION STEPS AND USE OF A RELATIVELY CHEAP, CONTINUOUSLY REGENERATED ABSORBENT WHICH HAS A HIGH CAPACITY FOR SO2 AS WELL AS A HIGH EFFICIENCY FOR SO2 REMOVAL.

Apnl 30, 1974 P. URBAN 3,808,324

CONTINUOUS PROCESS FOR SCRUBBING 50 FROM A GAS STREAM WTTH H REQENERATION AND CO STRIPPING Filed Aug. 17, 1971 1 T INVENTOR- Pefer Urban Scrubbing Zane l 1 ATTORNEYS United States Patent Oifice 3,808,324 Patented Apr. 30, 1974 US. Cl. 423-242 17 Claims ABSTRACT OF THE DISCLOSURE An input gas stream containing S is continuously treated in order to remove a substantial portion of the S0 therefrom by the steps of: (a) scrubbing the input gas stream with an aqueous absorbent stream containing an alkaline reagent; (b) treating the resulting rich absorbent stream with a gaseous mixture of H 8 and CO at conditions selected to convert the sulfite compound contained therein to the corresponding thiosulfate compound and to produce a gas stream enriched in CO content; (c) catalytically reacting the resulting thiosulfate compound with hydrogen at reduction conditions selected to produce a liquid stream containing the corresponding sulfide compound; (d) adding CO to the gas stream from step (b) to make a stripping gas; (e) stripping hydrogen sulfide from the liquid stream produced in step (c) by countercurrently contacting the liquid stream with the resulting stripping gas to form a regenerated aqueous absorbent stream and an overhead gas stream containing H 5 and CO (f) passing at least a portion of the regenerated absorbent stream to the scrubbing step and (g) passing at least a portion of the overhead gas stream from step (d) to step (b). The principal utility of this scrubbing process is associated with the problem of continuously removing a sulfur dioxide contaminant from the flue or stack gas streams such as are typically pro duced in modern electrical power generating stations in order to abate a serious pollution problem and to enable the safe, nonpolluting burning of high sulfur fuels. Key features of this process are: selective conversion of the sulfite compound obtained from the scrubbing step to the corresponding thiosulfate compound in the preliminary treatment step using a portion of a subsequently produced H S product stream, reduction of the resulting thiosulfate compound to the corresponding sulfide compound in a highly efiicient economic and selective manner, stripping of H 8 with a specially prepared C0 stream, minimization of undesired sulfate by-products during all of these conversion steps and use of a relatively cheap, continuously regenerated absorbent which has a high capacity for S0 as well as a high efficiency for S0 removal.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a continuation-in-part of my prior, copending application entitled Treating a Water Stream Containing a Water-Soluble Sulfite Compound which was filed Aug. 31, 1970 and assigned Ser. No. 68,274 now US. Pat. 3,635,820.

DISCLOSURE The subject of the present invention is a novel, continuous process for the selective removal of S0 from a gas stream containing same. More precisely, the present invention involves an SO -scrubbing step operated with an aqueous absorbent containing an alkaline reagent coupled with a unique regeneration procedure which comprises: a preliminary treatment step wherein sulfite compound contained in the rich scrubbing solution are converted to the corresponding thiosulfate compound, by a selective reaction with H 8, a primary reduction step wherein the resulting thiosulfate compound is catalytically converted by reaction withH to the corresponding sulfide compound, and a stripping step wherein the absorbent solution is regenerated by reaction with CO with liberation of hydrogen sulfide. In one important aspect, the present invention has to do with a scrubbing process which is operated with highly efii'cient aqueous absorbent comprising ammonium bicarbonate and/ or carbonate wherein the rich scrubbing solution withdrawn from the scrubbing step contains ammonium sulfite and/ or ammonium bisulfite wherein the preliminary treatment step involves a selective reaction of the ammonium sulfite and/ or ammonium bisulfite with a gas stream containing H 8 and CO to produce ammonium thiosulfate, wherein the primary reduction step involves selective catalytic reduction with hydrogen of the resulting ammonium thiosulfate to ammonium sulfide and/or hydrosulfide and wherein H Sis stripped from the resulting solution with CO a portion of which comes from the preliminary treatment step, to form the regenerated absorbent and at least a portion of the H 8 used in the thiosulfate formation reaction.

A major problem encountered in many areas of industry today is associated with the production of waste gas streams containing sulfur dioxide. The problem essentially involves the disposal of these waste gas streams without causing substantial air pollution. This problem is an extremely complex one because of the Wide variety of industrial sources that emit these sulfur dioxide-containing gas streams. One of the more common sources is associated with the combustion of sulfurcontaining fuels in boilers, internal combustion engines, heating units, etc., to produce flue or stack gas streams containing significant amounts of sulfur dioxide. Similarly, Waste gas streams of this type are generally produced by other industrial processes such as the smelting of sulfur-bearing ores, the refining of coke, the production of sulfur in a Claus process, the production of paper via a wood pulping process and the like industrial processes. It is well known that the indiscriminate discharge of these gas streams into the atmosphere results in a substantial air pollution problem because the sulfur dioxide has extremely detrimental effects on animal and plant life. In addition, the discharge of these gas streams into the atmosphere constitutes a waste of a valuable material because the sulfur contained in same is an industrial commodity. Many processes have been proposed for removal of sulfur dioxide from these gas streams. A large percentage of these proposed removal procedures involve contacting the sulfur dioxide containing gas stream with an aqueous absorbent stream which typically contain materials which chemically or physically react with the sulfur dioxide in order to absorb same into the liquid solution. A widely studied procedure involves the use of a solution of an alkaline reagent such as ammonium hydroxide or carbonate, one of the alkali or alkaline earth metal salts such as sodium hydroxide or carbonate, potassium hydroxide or carbonate and the like alkaline reagents, to produce a rich absorbent stream containing the corresponding sulfite and/ or bisulfite compound. For example, the use of an aqueous absorbent containing sodium bicarbonate and carbonate to form a rich scrubbing solution containing sodium sulfite and bisulfite.

Although the simple concept of the scrubbing S0 from the gas stream containing same with an aqueous absorbent containing an alkaline reagent has many advantages associated with it such as simplicity, high elfectiveness and versatility, wide spread adoption of this type of solution to the S0 pollution problem has been inhitbited by the lack of a regeneration procedure for the rich absorbent stream which can continuously regenerate the rich absorbent stream by selectively and economically converting the absorbed S to a conveniently handled and saleable product in a highly selected manner. That is, it is required that the regeneration procedure enable the operation of the scrubbing system in a closedloop manner with respect to the absorbent. In particular, it is required that an acceptable regeneration procedure have the capability of not only continuously producing a regenerated absorbent stream but also minimizing undesired byproducts so as to prevent the buildup of undesired intractable, difliculty removed ingredients in the absorbent stream once the system is operated in a closed-loop fashion. The byproduct that is of the greatest concern in this regard is sulfatefor example, in a system using an aqueous solution of ammonium hydroxide or ammonium carbonate as the absorbent, ammonium sulfate and bisulfate salts once formed in the system can present serious problems if special means are not provided to remove them or their production is not suppressed. Specifically, these salts can build up until finely divided solids are formed which then can cause corrosion, errosion and fouling problems.

One solution that has been proposed to the problem of regenerating the rich absorbent streams of the types discussed above in the use of the suitable reducing agent to react with the sulfite compounds contained therein in order to selectively produce elemental sulfur'and/or the corresponding sulfide compound. However, despite stringent precautions, when common reducing agents such as hydrogen, a suitable sulfide compound, or carbon monoxide are used in an attempt to directly reduce these sulfite compounds to elemental sulfur or the corresponding sulfide compounds, undesired sulfate compounds are formed in unacceptable amounts. These sulfate compounds are believed to be caused by the sulfite compounds undergoing auto-oxidation-reduction at the conditions necessary for direct reduction.

The problem addressed by the present invention is, therefore, to provide a fiue gas scrubbing system which is capable of continuous operation with a closed-loop absorbent circuit, which can selectively produce an easily removed substance as the principal product of the regeneration section and which can minimize the amount of undesired sulfate byproducts formed in the regeneration section.

I have now found a combination process for continuously scrubbing S0 from a gas stream which utilizes a conventional aqueous absorbent stream in a closedloop fashion and which comprises a Wet scrubbing step coupled with a novel regeneration procedure which en ables the recovery of hydrogen sulfide in high yield, minimizes undesired sulfate byproducts from the regeneration section and produces a regenerated absorbent stream which is of a relatively low total sulfur contentand, consequently, possesses a high capacity for S0 removal. The concept of the present invention is based on my finding that the sulfite compound contained in the rich scrubbing solution withdrawn from the scrubbing step can be easily converted at relatively low severity conditions to the corresponding thiosulfate compound by a selective reaction with H S without forming any substantial amounts of undesired, intractable sulfate compounds. Coupled with the finding are my additional observations that the thiosulfate compound can be catalytically reduced by hydrogen in a highly selective, economic and efiicient manner to form the corresponding sulfide compound and that hydrogen sulfide can be easily stripped from the resulting solution with a cO -containing stripping gas. Thus the central point of the present process involves using a conventional scrubbing procedure coupled with a regeneration procedure wherein thiosulfate is used as an intermediate in a multi-step operation designed to convert the sulfite compound contained in the rich absorbent stream to hydrogen sulfide, rather than an attempt to directly reduee the s lfi e c mpound to sulfide in a single step operation. This sulfite-to-thiosulfate-to-sulfide route provides a regeneration procedure which facilitates careful control of byproduct formation during the regeneration operation and enables the production of a regenerated absorbent stream which can be directly recycled to the scrubbing step, thereby allowing the system to be operated in the closed loop fashion with respect to the absorbent stream.

It is accordingly, an object of the present invention to provide a simple, effective, efiicient, and selective procedure for treating a gas stream containing S0 which process can selectively produce hydrogen sulfide and operate with a continuous closed-loop circuit of absorbent between the scrubbing section and the regeneration section. Another object is to minimize the amount of undesired, intractable byproducts formed in the regeneration section of such a procedure. Another object is to provide a regeneration procedure for an SO -scrubbing step that maximizes the sulfur dilferential across the regeneration procedure, thereby increasing the capacity and efficiency of the regenerated absorbent.

In brief summary, one embodiment of the present invention is a process for treating an input gas stream containing S0 in order to continuously remove a substantial portion of the S0 therefrom. The first step is a scrubbing step wherein the input gas stream is contacted in a suitable liquid-gas contacting zone with an aqueous absorbent stream containing an alkaline reagent at scrubbing condition selected to result in a treated gas stream containing a substantially reduced amount of S0 and in an effluent water stream containing a water-soluble sulfite compound. The next step is a preliminary treatment step which involves reacting at least a portion of the effiuent stream from the scrubbing step with a gas stream containing H 8 and CO at thiosulfate production conditions selected to form a liquid eflluent stream containing a thiosulfate compound and a C0 containing gas stream. Thereafter, the liquid efiiuent stream from the preliminary treatment step is catalytically reacted with hydrogen in the primary reduction step at reduction conditions selected to produce a sulfide-containing liquid efiluent stream. CO is then admixed with the CO -containing gas stream formed in the preliminary treatment step in order to prepare a stripping gas stream. The next step is a stripping step wherein hydrogen sulfide is stripped from the liquid efiiuent stream from the primary reduction step by countercurrently contacting it with the stripping gas to produce an H S- and CO containing overhead gas stream and a regenerated aqueous absorbent stream. In the final step, at least a portion of the resulting overhead gas stream is passed to the preliminary treatment step in order to supply H 8 reactant therefore, and at least a portion of the resulting regenerated aqueous absorbent stream is passed to the scrubbing step, thereby providing a closed-loop flow circuit of absorbent.

In another embodiment, the invention is a process as outlined above in the first embodiment wherein the alkaline reagent utilized in the aqueous absorbent stream is selected from the group consisting of the carbonate and bicarbonate salts of ammonia, the alkali metals and the alkaline earth metals which hydrolize in water to form a basic solutionfor example, ammonium carbonate, sodium carbonate and the like.

In a more specific embodiment, the present invention is a process for treating a gas stream containing S0 in order to remove a substantial portion of the S0 therefrom. The first step in this embodiment involves a scrubbing step in which the input gas stream is contacted with an aqueous absorbent containing ammonium bicarbonate or carbonate at scrubbing conditions selected to form a treated gas stream containing a substantially reduced amount of S0 and an effluent water stream containing ammonium sulfite or bisulfite. At least a portion of the efiluent water stream from the scrubbing step is th r after reacted, in a preliminary treatment step, with a gas stream containing H S and at thiosulfate production conditions selected to result in a liquid efiiuent stream containing ammonium thiosulfate and a CO -rich gas stream. The primary reduction step then involves catalytically reacting the liquid effluent stream from the preliminary treatment step with a hydrogen stream at reduction conditions selected to produce a liquid efliuent stream containing ammonium sulfide or hydrosulfide. The gas stream from the preliminary treatment step is then combined with additional CO to make a stripping gas stream. The liquid effluent stream from this primary reduction step is thereafter subjected to countercurrent contact with the stripping gas at stripping conditions effective to produce a regenerated aqueous absorbent stream containing ammonium bicarbonate or carbonate and an overhead gaseous stream containing H and C0 The final step then involves passing at least a portion of overhead gaseous stream from the stripping step to the preliminary treatment step and passing at least a portion of the resulting regenerated absorbent stream to the scrubbing step, thereby providing a closed-loop flow circuit of absorbent.

Yet another embodiment of the present invention involves a process as outlined above in the first embodiment wherein the primary reduction step is performed in the presence of a catalyst comprising a catalytically effective amount of a metallic component selected from the group consisting of the transition elements of Groups VI and VIII of the Periodic Table, and compound thereof, combined with a porous carrier material.

Other objects and embodiments of the present invention are hereinafter disclosed in the following detailed discussion of the input streams, the preferred conditions, the preferred reactants, the output streams and mechanics associated with each of the essential and preferred steps of the present invention.

The starting point for the subject process is a scrub bing step wherein an input gas stream containing S0 is contacted in a suitable gas-liquid contacting means with an aqueous absorbent stream containing an alkaline reagent. As previously explained, the input gas stream passed to this step is typically a flue or stack gas. For example, a typical stack gas stream containing about 1 to about 0 about 5 to or more CO about 3 to about 10% or more H O, about 0.01 to about 1% or more S0 In many cases, the input gas stream will also contain carbon monoxide, oxide of nitrogen, entrained fly ash and the other well known ingredients for flue gas streams. The amount of S0 contained in this input gas stream can vary over a wide range; namely from about 0.01 to about 1 mole percent or more, with a more typical amount being about 0.05 to about 0.5 mole percent. In many cases, this input gas stream is available at a relatively high temperature of about 200 to about 500 F. or more, and since it is preferred that the temperature of the input gas stream be at a relatively low level because this increases the capacity of the absorbent solution, it is often advantageous to cool the input gas sream by any suitable means such as by presaturating it with water under adibatic conditions.

The aqueous absorbent stream utilized in this scrubbing step is 'gdnerally characterized as an aqueous solution of a suitable water-soluble alkaline reagent which reacts with water to give a basic solution (i.e. one more basic than a solution of S0 in H O) such as ammonium hydroxide, ammonium carbonate and bicarbonate, the alkali metal hydroxides, the alkali metal carbonates and bicarbonates and the water-soluble alkaline earth metal hydroxide, carbonates and bicarbonates, and the like alkaline reagents. 0f the alkali metal reagents, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate are particularly preferred. In most cases, excellent results are obtained when the alkaline reagent is ammonium hydroxide or ammonium carbonate or ammonium bicarbonate. It is to be noted that it is within the purview of the present invention to use a mixture of the alkaline reagents previously mentioned. Since it is also contemplated that the scrubbing step can be operated with the absorbent continuously cycling around the scrubbing means, it is possible that absorbent could accumulate substantial amounts of sulfite and bisulfite compounds. In this last case, only a small portion of the rich efiluent stream from the scrubbing step would be sent to the regeneration section of the process, and the major portion of the rich absorbent withdrawn from the scrubbing step would be commingled with the regenerated absorbent stream and recycled to the scrubbing step.

The amount of alkaline reagent contained in the scrubbing solution is subject to some choice depending upon the specific requirements associated with the particular gas stream being treated; ordinarily, acceptable results are obtained when the alkaline reagent comprises about 1 to about 50 wt. percent of the absorbent solution, and more preferably to 1 to about 15 Wt. percent. Of course, absorbent solutions containing an amount of the alkaline reagent up to the solubility limit of the particular alkaline reagent selected at the conditions maintained in the scrubbing step can be utilized if desired. In the case where the absorbent is continuously cycled around the scrubbing step and only a drag stream drawn off for regeneration, the total amount of the alkaline reagent contained in the solution (i.e. fresh and spent) can reach rather high levels; for example, it can easily constitute 30 to 50 wt. percent of the absorbent solutions.

This scrubbing step can be carried out in a conventional scrubbing zone in any suitable manner including multiple stages. The scrubbing solution can be passed into the scrubbing zone in either upward or downward flow and the input gas stream can "be simultaneously introduced into the scrubbing zone in concurrent flow relative to the scrubbing solution. A particularly preferred procedure involves downward flow of the scrubbing solution with countercurrent flow of the gas stream which is to be treated. The scrubbing zone is preferably a conventional gas-liquid contacting zone containing suitable means for effecting intimate contact between a descending liquid stream and an ascending gas stream. Suitable contacting means include bubble trays, bafiles, and any of the various packing materials known to those skilled in the art. In this countercurrent mode of operation, a treated gas stream is withdrawn from the upper region of the scrubbing zone and a rich absorbent solution is withdrawn from the lower region thereof. For the class of alkaline reagents of concern here, the rich absorbent solution will contain substantial amounts of a water-soluble sulfite compound such as ammonium sulfite and/or bisulfite, sodium sulfite and/or bisulfite and the like. As indicated previously, according to one mode of operation of the scrubbing step, only a drag stream from the rich absorbent withdrawn from the step is sent to the regeneration section of the process; the rest is cycled around the scrubbiing step. The drag stream is ordinarily withdrawn at a rate at least suflicient to continuously remove the net sulfur taken up in the scrubbing step.

This scrubbing step is generally conducted under conventional scrubbing conditions which are selected on the basis of the characteristics of the specific alkaline reagent utilized, the sulfur dioxide content of the input gas stream, the portion of the sulfur dioxide that is to be removed in the scrubbing step, and the physical properties of the scrubbing zone. Ordinarily, the scrubbing step is preferably operated at a relatively low temperature of about 10 to C., relatively low pressure which typically approximates atmospheric (although better results are obtained at higher pressures), a volume ratio of input gas streams to scrubbing solution of about 100:1 to about 10,000:1 and a pH of about 4 to 7 or more. When the input gas stream is a flue or stack gas stream, means must ordinarily be provided for cooling the input gas stream to a relatively low temperature before it is introduced into the scrubbing step. Likewise, since the typical oper-- ation of the scrubbing step involves the handling of large volumes of gas containing only a relatively small amount of sulfur dioxide, it is preferred that the pressure drop through the scrubbing zone be held to a minimum so as to avoid the necessity of compressing large volumes of gas to overcome the pressure drop within the scrubbing zone.

Following the scrubbing step, the next step of the present process is the preliminary treatment step and it involves the conversion, in the highly selective manner, of the sulfite or bisulfite compound contained in at least a portion of the efiluent water stream withdrawn from the scrubbing step, to the corresponding thiosulfate compound. Ordinarily the sulfite or bisulfite compound is contained in the feed stream to this step in an amount of about 0.01 wt. percent, calculated on an equivalent sulfur basis, up to the solubility limit of the particular sulfite compound in water at the conditions utilized in the scrubbing step; for example, the feed stream to this step can contain about 1 to about 20 wt. percent or more sulfur as ammonium sulfite and/or bisulfite. According to the present invention, this step involves a reaction between the sulfite compound contained in this rich absorbent stream and a gas stream containing H 5 and CO Moreover, it is a feature of the present process that, after start-up of the process, this gas stream containing H 5 and CO is obtained from a subsequently described stripping step. The active ingredient in this gas stream is H 5 and it acts as a reducing agent with respect to the sulfite contained in the absorbent stream. The amount of this sulfide reactant utilized in this step is at least sufficient to provide 0.5 mole of sulfide compound per mole of sulfite compound contained in the rich absorbent stream, with best results obtained at a mole ratio corresponding to about 0.621 to about 1.5 :1 or more. Like wise, good results are ordinarily obtained when the pH of the effluent water stream is in the range of 4 to about 7 or more.

Conditions utilized in this preliminary treatment step can be generally described as thiosulfate production conditions and comprise: a temperature of about 20 to about 150 C., a pressure suflicient to maintain the efiiuent water stream in the liquid phase and a contact time corresponding to about 0.05 to 1 or more hours. For example, excellent results have been obtained at a temperature of 65 C., a pressure of 50 p.s.i.g., a contact time of 5 minutes, sulfide to sulfite mole ratio of 1.1:1, and a pH of 9.

Following this preliminary treatment step, a liquid effluent stream containing relatively large amounts of a thiosulfate compound is withdrawn therefrom and passed to the primary reduction step of the present process wherein it is catalytically treated with hydrogen at reduction conditions selected to produce the corresponding sulfide compound. Also withdrawn from this preliminary treatment step is a gas stream containing CO This gas stream is relatively rich in CO because substantially all of the H 8 originally contained therein is reacted out in this preliminary treatment stepfor example, a typical input gas stream to this step would contain 92% CO and 8% H 5, with the exit gas containing greater than 99% C0 The primary reduction step is effected by contacting the liquid efiluent stream and a hydrogen stream with a suitable reduction catalyst at reduction conditions selected to reduce the thiosulfate compound contained in this efiluent stream to the corresponding sulfide compound and H 0. This step can be carried out in any suitable manner taught in the art for contacting a liquid stream and a gas stream with a solid catalyst. A particularly preferred method involves a fixed-bed catalyst system in which the catalyst is disposed in the reduction zone and the thiosulfate-eontaining liquid stream is passed therethrough in either upward, radial, or downward flow with a hydrogen stream being simultaneously introduced in either countercurrent or concurrent flow relative to the aqueous stream. In particular, a preferred embodiment involves downflow and concurrent flow of the aqueous stream and the hydrogen stream through the reduction zone.

This reduction step can, moreover, be carried out with any suitable reduction catalyst known to be capable of reducing a thiosulfate compound to the corresponding sulfide compound. Based on my investigations I have determined that particularly good results are obtained with a catalyst comprising a catalytically effective amount of a metallic component selected from the group consisting of the transition metals of Groups VI and VIII such as chromium, molybdenum, tungsten, iron, cobalt, nickel, platinum, palladium, iridium, etc. combined with a suitable porous carrier material. More specifically, preferred catalysts for the desired reduction reaction comprise a combination of a catalytically effective amount of a Group VI or Group VIII transition metal component with a suitable porous support such as alumina or activated carbon. Of the transition metals, the ones best suited for the present process are the iron group metals of Group VIII; specifically, iron, cobalt, nickel and compounds thereof. Particularly preferred embodiments of the present process involve the use of catalysts in which the metallic component is present in the form of a metallic sulfide such as cobalt sulfide, iron sulfide, nickel sulfide, molybdenum sulfide, or tungsten sulfide combined with a carrier material. The preferred carrier materials are activated carbons or charcoals such as those commercially available under the trade names of Norite, Nuchar, Darco and other similar products. In addition, conventional natural or synthetic highly porous inorganic refractory oxide carrier materials may be used as the support for the metallic component such as alumina, silica-zirconia, silica alumina, bauxite, clay, etc. Best results are ordinarily obtained with a catalyst comprising an iron group metallic component combined with relatively small particles of a suitable solid carrier material. That is, exceptionally good results are obtained with a catalyst having a metallic component selected from the compound and metals of iron, cobalt and nickel, with the oxides and sulfides of these metals being especially preferred. Excellent results are obtained when the reduction catalyst is a catalytically effective amount of cobalt sulfide combined with a suitable refractory inorganic oxide carrier material such as alumina, or cobalt sulfide combined with activated carbon.

An acceptable method for making this reduction catalyst comprises impregnating the carrier material with an aqueous solution of a soluble salt of the metallic component such as the acetate salt, the chloride salts, the nitrate salts, etc. The metallic component of the resulting composite can then be converted to the sulfide by treatment with hydrogen sulfide preferably at room temperature. The resulting sulfided composite is thereafter washed with an aqueous and/ or ammoniacal solution and dried. In the case where the carrier material is a refractory inorganic oxide, it may be advantageous to calcine or oxidize the impregnated carrier material at a relatively high temperature to obtain distribution of the metallic component on the carrier material which can thereafter be sulfided with a suitable sulfur compound in order to obtain the desired catalyst.

"In general, the metallic component is preferably combined with the carrier material in an amount suflicient to result in the reduction catalyst containing about 0.1 to about 25 wt. percent of the metallic component, calculated as the elemental metal. For the preferred cobalt sulfide catalyst, the amount of cobalt incorporated is preferably in an amount sufficient to result in a reduction catalyst containing about 1 to about 10 wt. percent cobalt.

An essential reactant for the primary reduction step is hydrogen. The hydrogen stream charged to the primary reduction step may be substantially pure hydrogen or a mixture of hydrogen with other relatively inert gases, such as a mixture of hydrogen with C to C hydrocarbons, a a mixture of hydrogen and nitrogen, a mixture of hydrogen and carbon dioxide, a mixture of hydrogen and hydrogen sulfide, etc. The excess recycle gas obtained from various petroleum processes which have a net hydrogen make, such as a reforming process, a dehydrogenation or dehydrocyclization process, etc., may also be used if desired. It is preferred that the hydrogen be utilized in an amount equivalent to or greater than the stoichiometric amount required for the reduction of thiosulfate to sulfide. The stoichiometric amount is 4 moles of hydrogen per mole of thiosulfate. In general, it is preferred to operate at a hydrogen to thiosulfate mole ratio substantially greater than this stoichiometric amount. Hence, about 4 to about 100 moles of hydrogen per mole of the thiosulfate compound contained in the aqueous stream charged to the reduction step is preferably used; with best results obtained at a mole ratio of about 20:1 to about 50:1. It is understood that any unreacted hydrogen may be recovered from the effluent from this reduction step and then can be recycled, if desired, through suitable compressive means to supply at least a portion of the necessary hydrogen for the reduction step as is shown in the attached drawing.

The conditions utilized in this primary reduction step are generally described as reduction conditions effecting conversion of thiosulfate to sulfide. The temperature utilized is preferably selected from the range of about 125 to about 350 C. The pressure employed is typically a pressure which is suflicient to maintain the aqueous stream containing the thiosulfate compound in liquid phase. In general, it is preferred to operate at superatmospheric pressures and preferably a pressure of about 100 to about 3,000 p.s.i.g. Moreover, it is preferred to use a liquid hourly space velocity (defined on the basis of the volume charge rate of the aqueous stream divided by the total volume of the reduction catalyst within the reduction zone) ranging from about 0.5 to about hrs. with best results obtained at about 1 to about 3 hrs- 'In a preferred embodiment of the primary reduction step wherein the aqueous stream containing the thiosulfate compound and the hydrogen stream are concurrently contacted with the reduction catalyst, the efiiuent stream withdrawn from the reduction zone contains the sulfide product of the reduction reaction, a very minor amount of unreacted thiosulfate, unreacted hydrogen, water and the alkaline reagent. For example in the case where the aqueous stream contains ammonium thiosulfate, the sulfide product of reduction reaction is typically present as ammonium hydrosulfide or as hydrogen sulfide or a mixture of these, with the amount of ammonium hydrosulfide present therein depending primarily upon the amount of ammonia present in the infiuent to the reduction step. Unreacted hydrogen is typically separated from the efiluent stream from the reduction step in a separating zone and recycled to the reduction zone. Also recovered from the separating zone is the liquid portion of the efiluent stream from the primary reduction step; it contains the sulfide product of the reduction reaction.

In the next step of the present invention the liquid efiluent stream recovered from the primary reduction step is subjected to a stripping step designed to liberate hydrogen sulfide therefrom. Although any suitable stripping gas can be utilized including steam, nitrogen, air and the like, carbon dioxide is particularly preferred, because it acts to decrease the pH of the solution and form the corresponding carbonate salt. For instance, in the case where the efiiuent stream from the primary reduction step contains ammonium hydrosulfide, stripping with carbon dioxide liberates hydrogen sulfide and produces a regenerated absorbent stream containing ammonium bicarbonate. According to the present invention, at least a portion of the CO necessary for this stripping step is derived from the efiiuent gas stream recovered from the preliminary treatment step. I

10 have observed that this gas stream provides a superior component of the stripping gas used in this stripping step because the reaction between sulfite and sul'fide occurring in the preliminary treatment step acts to enrich the CO content of the exit gas stream from this treatment step. It is, accordingly, a feature of the present invention that the re quired stripping gas is prepared by admixing carbon dioxide with the CO -rich gas stream produced in the preliminary treatment step. The amount of outside CO that is added to this mixture is dependent on the amount of CO contained in the CO -rich gas stream recovered from the preliminary treatment step and the amount of sulfide contained in the liquid efiiuent from the primary reduction step. In general, the amount of CO added should be sufficient to insure that the mole ratio of C0,, to sulfide charged to the stripping step is maintained substantially above 0.5: l, and preferably in the range of 1:1 to 10:1 or

' more.

This stripping step is accomplished by countercurrently contacting the liquid eflluent stream from the primary reduction step with the stripping gas stream at suitable H 8 stripping conditions. In general, superior results are obtained when this step is performed at a relatively low temperature and at a relatively high pressure. For example, excellent results are obtained in this step at a temperature of 40 C., a pressure of 200 p.s.i.g. and a mole ratio of CO to sulfide of 5:1. This step is operated to produce an overhead gas stream containing H 8 and CO with H O in many casesand a bottom stream comprising the regenerated aqueous absorbent.

This regenerated aqueous absorbent stream is substantially reduced in total sulfur content relative to the input rich absorbent stream and usually will contain less than 10% of the amount of sulfur contained in the in ut absorbent stream. Because carbon dioxide is utilized in the stripping step as the stripping medium, this regenerated absorbent stream Will contain substantial amounts of the carbonate or bicarbonate salt of the alkaline reagent originally present in the input absorbent stream--for example in the case where the alkaline reagent is ammonia, the regenerated absorbent stream will contain ammonium carbonate and/or bicarbonate, and in the case when the alkaline reagent is sodium hydroxide or carbonate the treated water stream will contain sodium carbonate and/ or bicarbonate.

In accordance with the instant process, at least a portion of the regenerated absorbent stream is passed or recycled to the S0 scrubbing step. Similarly a portion of the H S- and Co -containing overhead gas stream produced in the stripping step is passed to the preliminary treatment step in order to supply at least a portion of the H 8 reactant used therein. The remaining portion of this hydrogen sulfide-containing stream is then recovered as one of the product streams from the instant process. The hydrogen sulfide contained in this product stream can be converted to elemental sulfur by any suitable oxidation procedure such as a conventional Claus process or to sulfuric acid or used per se.

Having broadly characterized the essential steps comprising the present process, reference is now made to the attached drawing for a detailed explanation of a working example of a preferred flow scheme for the present invention. The attached drawing is merely intended'as a general representation of the flow scheme involved with no intention to give details about heaters, pumps, valves, and the like equipment except where a knowledge of these devices is essential to an understanding of the present invention or would not be self-evident to those skilled in the relevant art.

Referring now to the attached drawing, a fiue gas stream enters the system via line 1 and is passed into the lower region of a conventional liquid-gas scrubbing means, zone 2. In this zone it is passed in countercurrent flow to a descending stream of absorbent solution which enters the upper region of zone 2 via line 4. The input gas stream contains about 5% O 12% C 6% H O, 76.8% N and 0.2% S0 Zone 2 is a conventional-gas liquid contacting zone fitted with conventional means such as baflles, trays, packing material and the like, for effecting intimate contact between an ascending gas stream and a descending liquid stream. The resulting treated gas stream is Withdrawn from zone 2 via line 3.

Also introduced into zone 2 is a liquid stream comprising the aqueous absorbent solution. It enters zone 2 via line 4 and is made up of two separate streams, one of which is a regenerated absorbent stream obtained from the regeneration section of the present system and the second of which is a major portion of the rich absorbent stream withdrawn from the lower region of zone 2 via line 4. The alkaline reagent utilized in this absorbent stream is primarily ammonium carbonate with a minor amount of ammonium bicarbonate.

According to the mode of operation of zone 2 shown in the drawing, the rich absorbent stream is withdrawn from the bottom of zone 2 via line 4 and a major portion of this stream is continuously cycled around zone 2 in order to allow the concentration of sulfite salts in the absorbent stream to build to relatively high levels. This procedure increases the capacity of the absorbent and minimizes the amount of the absorbent stream that must be cycled through the regeneration section of the system. The absorbent stream introduced into scrubber 2 via line 4 will, accordingly, contain a substantial amount of sulfite salts along with the alkaline reagent. Ordinarily, zone 2 is operated by monitoring the pH of the absorbent stream at the inlet to zone 2 and controlling the amount of the rich absorbent stream diverted to the regeneration section of the system at the junction of line 4 and in response to a decrease in pH level. The preferred pH range is about 4 to about 7 or more, with best results ordinarily obtained in the range of about 5 to 7. With the system operating so that the absorbent stream introduced into zone 2 via line 4 is maintained at a pH level within this range, the rich absorbent stream withdrawn continuously from zone 2 via line 4 can typically contain about 1 to about 15 or more wt. percent sulfur principally as a mixture of ammonium sulfite and ammonium bisulfite. In addition, minor amounts of ammonium sulfate and thiosulfate are formed in zone 2. In the particular case shown in the drawing, the rich absorbent preferably contains about 8 wt. percent sulfur as ammonium sulfite and bisulfite.

Zone 2 is operated at a temperature of about 50 C., a pressure of about atmospheric and a gas to absorbent volume ratio of about 500:1. At these conditions, the treated gas stream withdrawn from the upper region of zone 2 via line 3 is found to contain less than 5% of the S0 originally present in the input gas stream.

The rich absorbent stream Withdrawn from the lower region of zone 2 via line 4 is divided into two portions at the junction of line 5 with line 4. The major portion continues on via line 4 and is admixed with regenerated absorbent at the junction of line 18 with line 4. The resulting mixture of cycled and regenerated absorbent is then reintroduced into zone 2 via line 4. The minor por tion of the rich absorbent is passed via line 5 into the first reacting zone, zone 6. The amount of rich absorbent passed into zone 6 is ordinarily at least sufiicient to remove the net sulfur input into zone 2 from the input gas stream in order to line out the concentration of sulfur in the absorbent stream. In the case under consideration, the amount of the absorbent withdrawn for regeneration via line 5 will be about 0.1 to 10% of the rich absorbent stream withdrawn from the bottom of zone 2. It is to be noted that during start-up of scrubbing zone 2, the inventory of the scrubbing solution needed for initiating operation is introduced into the system via line 20, 18 and 4. It is also to be recognized that there is a net water make in the regeneration section of the system due to the reaction of ammonium thiosulfate with hydrogen. At

least a portionof the net water product of the present process can be removed from the system in the treated gas stream withdrawn via line 3 if the input gas stream entering the process via line 1 is not saturated with water. If the amount of Water withdrawn from the system via line 3 is not sufficient to remove the net water make, a portion of the regenerated absorbent can be removed from the system via line 19 and treated in a conventional manner to separate water therefrom with recycle of recovered alkaline reagent if desired.

The rich absorbent stream introduced into zone 6 via line 5 in the particular case of concern here contains about 8 wt. percent sulfur as a mixture of ammonium sulfite and ammonium bisulfite. It is heated to a temperature of about 65 C. by heating means (not illustrated) prior to passage into zone 6. Zone 6 is a conventional liquid-gas contacting zone designed to effect 1nt1mate contact between an ascending stream enters the upper region of zone 6 and flows downwardly to an exit port located in the bottom region of the zone. Also introduced into the lower region of zone 6 is a gas stream containing a mixture of H 8 and CO This gas stream flows upwardly through the descending liquid stream to an exit port in the upper region of the zone whereat it is withdrawn from the zone via line 21. During start-up of this zone sufficient H 5 is introduced via lines 17 and 15 to initiate the desired reaction; thereafter, a portion of an H S- and CO -containing overhead gas stream, which is produced in a subsequently described stripping step, is passed to zone 6 from zone 14 via line 15. Regardless of the source of the reducing agent charged to zone 6, it is passed thereto in an amount at least sufficient to react about 0.5 mole of H 8 per mole of sulfite charged to zone 6. It is to be noted that amounts of H 8 in excess of this minimum amount can be beneficially utilized because excess H 8 is absorbed at least in part into the liquid stream being treated and this absorbed H 8 will materially aid the reaction occurring in subsequently described zone 8.

Zone 6 is maintained at thiosulfate production conditions which in this particular case are a temperature of about 65 C., a pressure of about 200 p.s.i.g. and a residence time of the liquid stream in zone 6 of about 0.1 hr.

An overhead gas stream containing relatively large amounts of CO and very minor amounts of H S is then withdrawn from zone 6 via line 21 and passed to the junction of line 21 with line 22 whereat it is admixed with additional CO which enters the system via line 22. The resulting mixture then passes to zone 14 via line 21. A liquid effluent stream is withdrawn from the bottom of zone 6 via line 7, heated to a temperature of about 200 C. by heating means (not shown) and charged to the second reaction zone, zone 8. This aqueous efiluent stream contains ammonium thiosulfate in an amount corresponding to a conversion in zone 6 of greater than of the entering ammonium sulfite and bisulfite to ammonium thiosulfate. Furthermore, the amount of undesirable ammonium sulfate formed by the selective reaction occurring within zone 6 is less than 3% of the input sulfite. Thus, the aqueous effiuent stream withdrawn from zone 6 principally contains ammonium thiosulfate with minor amounts of unreacted ammonium sufite and bisulfite and with trace amounts of ammonium sulfate. Because carbon dioxide is contained in the gas introduced into zone 6, this liquid effluent stream will also contain minor amounts of ammonium carbonate and bicarbonate.

The second reaction zone, zone 8, is another liquidgas reaction zone designed to affect intimate contact between a concurrently flowing hydrogen-containing gas stream, a liquid stream and a solid bed of a reduction catalyst. The liquid efiluent stream from zone 6 is introduced into the upper region of the zone 8 via line 7. Also introduced into the upper region of the zone 8 is an H containing gas stream where enters the zone by means of lines 11 and 7. After start-up of the process, a substantial portion of the necessary hydrogen is recycled hydrogen recovered from the effluent stream withdrawn from zone 8. During start-up of the process, sufiicient hydrogen is introduced into zone 8 via lines 12, 11 and 7 in order to provide a circulating inventory of hydrogen which flows around a flow circuit defined by lines 9, 11 and 7. After this inventory is provided, line 12 is utilized to inject makeup hydrogen into the system in order to maintain the desired mole ratio of H to thiosulfate Within zone 8. Zone 8 contains a catalyst comprising 12 to 20 mesh particles of Darco activated carbon having a cobalt sulfide component combined therewith in an amount sufficient to result in the catalyst containing 2.3 wt. percent cobalt. The catalyst is prepared by a conventional impregnation procedure with a water-soluble compound of cobalt followed by a sulfiding treatment at a relatively loW temperature. The total amount of hydrogen introduced into zone 8 corresponds to a hydrogen to ammonium thiosulfate mole ratio of 40:1. The reduction conditions maintained in zone 8 in this particular case are a temperature of 200 C., a pressure of 300 p.s.i.g. and liquid hourly space velocity of 2 hours- An efiluent stream comprising a mixture of liquid and gas is withdrawn from zone 8 via line 9, cooled to a temperature of about 100 C. by cooling means (not illustrated) and passed into separating zone 10. In zone 10, a hydrogen-rich gas phase separates from a liquid aqueous phase. The gas phase contains unreacted hydrogen, hydrogen sulfide and water vapor; it is withdrawn from zone 10 via line 11 and recirculated through a compressor (not shown) to zone 8. Zone 10 is operated at a pressure which is approximately the same as that utilized in zone 8.

The liquid phase formed in zone 10 is withdrawn therefrom via line 13, cooled to a temperature of about 40 C. by cooling means (not shown) and passed to the upper region of stripping zone 14. This liquid stream is the aqueous portion of the eflluent stream from zone 8 and it contains ammonium hydrosulfide, trace amounts of unreacted ammonium thiosulfate, ammonium hydroxide, ammonium bicarbonate and a minor amount of ammonium sulfate. An analysis of this aqueous stream indicates that 99% of the ammonium thiosulfate charged to zone 8 is converted therein, with 89% of this thiosulfate being converted to ammonium hydrosulfide. In addition, the analysis shows that less than of the ammonium thiosulfate is converted in zone 8 to the undesired, refractory ammonium sulfate.

In stripping zone 14, the aqueous effluent stream charged thereto is countercurrently contacted with an ascending stripping gas Which is introduced in the lower region of zone 14 by means of the line 21. The stripping gas is prepared by mixing CO with the overhead gas stream from zone 6 in an amount sufiicient to result in a mole ratio of CO to sulfide charged to zone 14 of 5:1. Zone 14 is operated in the conventional manner at a relatively low temperature of about 40 C. and a pressure of about 200 p.s.i.g. Zone 14 also typically contains suitable means for effecting intimate contact between a descending liquid stream and an ascending gas stream. Carbon dioxide is especially preferred for use as a stripping gas because it acts as to lower the pH of the liquid stream to the point where H 8 is released from the solution and ammonium carbonate or bicarbonate is formed; it also helps to eliminate problems of NH carry-over in the stripping gas stream. In some cases it is a preferred practice to inject into the top of zone 14, a portion of the bottom stream withdrawn therefrom via line 18 in order to minimize NH carry-over in the overhead gas stream.

An overhead gaseous stream is then withdrawn from zone 14 via line 15 and passed to the junction of line 16 with line 15. The major portion of this overhead stream is then Withdrawn from the system via line 16. The gas stream withdrawn via line 16 contains the net sulfide product of the present process and, it can be charged to any suitable process for the recovery of sulfur or the manufacture of sulfuric acid; for example, this stream could be passed to a conventional Claus unit for recovery of sulfur via an oxidation procedure. This overhead gaseous stream contains a relatively large amount of hydrogen sulfide, carbon dioxide and minor amounts of ammonia and water. Another portion of this overhead stream is passed via line 15 to zone 6 in order to supply the hydrogen sulfide reactant necessary for the conversion of sulfite to thiosulfate in zone 6 as explained hereinbefore.

A stream of regenerated absorbent is Withdrawn from the lower region of zone 14 via line 18 and passed back to zone 2 via lines 18 and 4. This regenerated absorbent stream primarily contains a mixture of ammonium carbonate and bicarbonate with minor amounts of unreacted ammonium thiosulfate, unreacted ammonium sulfite, ammonium hydrosulfide and ammonium sulfate. The total sulfur content of this regenerated absorbent stream is less than 10% of the total sulfur content of the rich absorbent stream withdrawn from the scrubbing section of the system via line 5. Moreover, the amount of undesired ammonium sulfate formed in the regeneration section of the system (i.e., the section of the system comprising zones 6, 8, 10 and 14) is less than 3% of the sulfite charged to the regeneration section via line 5. Thus the scrubbing process of the present invention enables the continuous scrubbing of S0 from the gas stream entering the system via line 1 with continuous regeneration and recirculation of absorbent in a closed-loop manner. In addition, the amount of undesired ammonium sulfate formed in the regeneration section of the system is held to extremely low levels.

It is intended to cover by the following claims all changes and modifications of the above disclosure of the present invention that would be self-evident to a man of ordinary skill in the gas treating art.

I claim as my invention:

1. A process for treating an input gas stream containing S0 in order to continuously remove S0 therefrom, said process comprising the steps of:

(a) contacting the input gas stream with an aqueous absorbent stream containing an alkaline reagent selected from the group consisting of ammonium, alkali metal and alkaline earth metal hydroxides, carbonates and bicarbonates at scrubbing conditions selected to result in a treated gas stream containing a reduced amount of S0 and in an effluent water stream containing a water-soluble sulfite compound;

(b) reacting at least a portion of the eflluent stream from step (a) with a gas stream containing H S and CO at thiosulfate production conditions selected to form a liquid effluent stream containing a thiosulfate compound and a Co -containing gas stream;

(0) catalytically treating the liquid effluent stream from step (b) with hydrogen at reduction conditions selected to produce a substantially thiosulfate-free liquid efiiuent stream containing a sulfide compound;

((1) adding CO to the Co -rich gas stream formed in step (b) to make a stripping gas;

(e) stripping hydrogen sulfide from the liquid eflluent stream produced in step (c) by countercurrently contacting the eflluent stream with the stripping gas from step (d) to form an H S- and Co -containing overhead gas stream and a regenerated aqueous absorbent stream; and thereafter,

(f) passing at least a portion of the resulting regenerated aqueous absorbent stream to step (a) and passing at least a portion of the overhead gas stream from step (d) to step (b).

2. A process as defined in claim 1 wherein the alkaline reagent is ammonium carbonate or ammonium bicarbonate.

3. A process as defined in claim 1 wherein the alkaline reagent is an alkali metal carbonate or alkali metal bicarbonate.

4. A process as defined in claim 3 wherein the alkali metal is sodium.

5. A process as defined in claim 3 wherein the alkali metal is potassium.

6. A process as defined in claim 1 wherein the alkaline reagent is a water-soluble alkaline earth metal carbonate or an alkaline earth metal bicarbonate.

7. A process as defined in claim 1 wherein the amount of hydrogen charged to step (c) is sufiicient to provide a mole ratio of hydrogen to thiosulfate passed thereto of at least 4:1.

8. A process as defined in claim 1 wherein the amount of H 5 charged to step (b) is at least sufiicient to provide a mole ratio of sulfide to sulfite in this step of 1:2.

9. A process as defined in claim 1 wherein step (c) comprises contacting the effluent stream from step (b) and a hydrogen stream with a reduction catalyst, comprising a combination of a catalytically effective amount of a metallic component, selected from the group consisting of the transition metals and compounds of Groups VI and VIII of the Periodic Table, with a porous carrier material, at reduction conditions selected to form a substantially thiosulfate-free aqueous effiuent stream containing a sulfide compound.

10. A process as defined in claim 9 wherein the metallic component of the reduction catalyst is selected from the metal and compounds of the iron group metals.

11. A process as defined in claim 9 wherein the iron group metallic component is cobalt or a compound of cobalt.

12. A process as defined in claim 11 wherein the reduction catalyst comprises a catalytically eifective amount of cobalt sulfide combined with activated carbon or alumina carrier material.

13. The process of claim 1 further characterized in that step (a) is effected at a temperature of from about to about 100 C., step (b) at a temperature of from about 20 to about 150 C. and step (c) at a temperature of from about 125 to about 350 C., steps (b) and (c) being under sufiicient pressure to maintain the efiluent streams treated therein in liquid phase.

14. The process of claim 15 further characterized in that step (a) is effected at a temperature of from about 10 to about 100 (3., step (b) at a temperature of from about to about 150 C., and step (c) at a temperature of from about 125 to about 350 0, steps (b) and (c) being under sulficient pressure to maintain the efliuent streams treated therein in liquid phase.

15. A process for treating an input gas stream containing S0 in order to continuously remove a substantial portion of the S0 therefrom, said process comprising the steps of:

(a) contacting the input gas stream with an aqueous absorbent stream containing ammonium bicarbonate or carbonate at scrubbing conditions selected to form a treated gas stream containing a reduced amount of S0 and an effiuent water stream containing ammonium sulfite or ammonium bisulfite;

(b) reacting at least a portion of the efiluent water stream from step (a) with a gas stream containing H 5 and CO at thiosulfate production conditions selected to result in a liquid efiluent stream containing ammonium thiosulfate and a CO -rich gas stream;

(0) catalytically treating the liquid efiiuent stream from step (b) with hydrogen at reduction conditions selected to form a substantially thiosulfate-free liquid efiluent stream containing ammonium sulfide or hydrosulfide;

((1) adding Co -rich gas stream formed in step (b) to make a stripping gas;

(e) countercurrently contacting the liquid efiluent stream from step (c) the stripping gas from step (d) to form an H S- and Co -containing overhead gas stream and a regenerated aqueous absorbent stream containing ammonium bicarbonate or carbonate; and thereafter,

(f) passing at least a portion of the resulting regenerated absorbent stream to step (a) and passing at least a portion of the H S- and CO -containing gas stream from step (d) to step (b).

16. A process as defined in claim 15 wherein hydrogen is charged to step (c) in an amount corresponding to a mole ratio of hydrogen to ammonium thiosulfate passed thereto of about 4:1 to about :1.

17. A process as defined in claim 15 wherein step (c) comprises contacting the efiluent stream from step (b) and a hydrogen stream with a catalyst, comprising a combination of a catalytically effective amount of cobalt sulfide with a porous carrier material, at reduction conditions selected to form a substantially thiosulfate-free aqueous efiluent stream containing ammonium hydrosulfide.

References Cited UNITED STATES PATENTS 3,431,070 3/19'69 Keller 423242 X 3,574,530 4/ 1971 Suriani et al 423242 3,627,470 12/ 1971 Hamblin 21063 X OSCAR R. VERTIZ, Primary Examiner G. A. HELLER, Assistant Examiner US. Cl. X.R. 210-59 

